Novel polyoxaalkyl aminoalcohols

This application is a division of application Ser. No. 296,214, filed Aug. 25, 1981, now U.S. Pat. No. 4,429,160, issued Jan. 31, 1984.

1. Field of the Invention

The present invention relates to novel polyoxaalkyl aminoalcohols, a process for the preparation thereof, and the complexation of cations therewith.

2. Description of the Prior Art

Certain polyoxaalkyl aminoalcohols are known to this art. Compare British Patent Specification No. 897,163 which relates to those aminoalcohols having the structural formula:

HO--alkylene--N--CH.sub.2 --CH.sub.2 --OCH.sub.2 --CH.sub.2).sub.x O--R].sub.2

wherein R is an alkyl radical having from 1 to 6 carbon atoms, and x is an integer ranging from 2 to 10.

These aminoalcohols may be prepared by reacting an alkanolamine, HO-alkylene-NH 2 , with, for example, an alkoxypolyethylene-oxyethyl chloride having the structural formula:

Cl--CH.sub.2 --CH.sub.2 --OCH.sub.2 --CH.sub.2).sub.x --O--R.

Compare also published German Patent Application No. 2,835,984, and published European Patent Application No. 5,094.

Accordingly, a major object of the present invention is the provision of novel and different aminoalcohols, said novel compounds being polyoxyalkyl aminoalcohols having the structural formula: ##STR2## wherein R 1 , R 2 , R 3 and R 4 , which may be identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms; R 5 is an alkyl, or phenyl substituted alkyl radical having from 1 to 12 carbon atoms, a cycloalkyl radical having from 3 to 12 carbon atoms, a phenyl, or alkyl substituted phenyl radical with said alkyl substituent having from 1 to 12 carbon atoms; n is an integer ranging from 1 to 9; and m is an integer ranging from 1 to 10.

More particularly according to this invention, preferred polyoxaalkyl aminoalcohols of the formula [I] are those in which R 1 , R 2 , R 3 and R 4 are either identical or different and are either hydrogen or methyl; R 5 is an alkyl radical having from 1 to 6 carbons, more preferably 1 to 4 carbon atoms, a cyclohexyl radical, a phenyl radical or a C 1 -C 4 alkyl substituted phenyl radical; n is an integer ranging from 1 to 5, more preferably ranging from 1 to 3; and m is an integer ranging from 1 to 6, more preferably ranging from 1 to 4.

Exemplary of the novel polyoxaalkyl aminoalcohols according to the invention are:

[1] N-(5'-Hydroxy-3'-oxapentyl)-5-aza-2,8-dioxanonane;

[2] N-(5'-Hydroxy-3'-oxapentyl)-6-aza-3,9-dioxanonane;

[3] -N(5'-Hydroxy-3'-oxapentyl)-7-aza-4,10-dioxatridecane;

[4] N-(5'-Hydroxy-3'-oxapentyl)-8-aza-5,11-dioxapentadecane;

[5] N-(5'-Hydroxy-3'-oxapentyl)-8-aza-2,5,11,14-tetraoxapentadecane;

[6] N-(5'-Hydroxy-3'-oxapentyl)-9-aza-3,6,12,15-tetraoxaheptadecane;

[7] N-(5'-Hydroxy-3'-oxapentyl)-10-aza-4,7,13,16-tetraoxanonadecane;

[8] N-(5'-Hydroxy-3'-oxapentyl)-11-aza-5,8,14,17-tetraoxaheneicosane;

[9] N-(5'-Hydroxy-3'-oxapentyl)-12-aza-3,6,9,15,18,21-hexaoxatricosane;

[10] N-(5'-Hydroxy-3'-oxapentyl)-13-aza-4,7,10,16,19,22-hexaoxapentacosane;

[11] N-(5'-Hydroxy-3'-oxapentyl)-14-aza-5,8,11,17,20,23-hexaoxaheptacosane;

[12] Those aminoalcohols having the structural formula: ##STR3## wherein m ranges from 1 to 3, and p ranges from 1 to 4; [13] N-(8'-Hydroxy-3',6'-dioxaoctyl)-5-aza-2,8-dioxanonane;

[14] N-(8'-Hydroxy-3',6'-dioxaoctyl)-6-aza-3,9-dioxaundecane;

[15] N-(8'-Hydroxy-3',6'-dioxaoctyl)-7-aza-4,10-dioxatridecane;

[16] N-(8'-Hydroxy-3',6'-dioxaoctyl)-8-aza-5,11-dioxapentadecane;

[17] N-(8'-Hydroxy-3',6'-dioxaoctyl)-8-aza-2,5,11,14-tetraoxapentadecane;

[18] N-(8'-Hydroxy-3',6'-dioxaoctyl)-9-aza-3,6,12,15-tetraoxaheptadecane;

[19] N-(8'-Hydroxy-3',6'-dioxaoctyl)-10-aza-4,7,13,16-tetraoxanonadecane;

[20] N-(8'-Hydroxy-3',6'-dioxaoctyl)-11-aza-5,8,14,17-tetraoxaheneicosane;

[21] N-(8'-Hydroxy-3',6'-dioxaoctyl)-11-aza-2,5,8,14,17,20-hexaoxaheneicosane;

[22] N-(8'-Hydroxy-3',6'-dioxaoctyl)-12-aza-3,6,9,15,18,21-hexaoxatricosane;

[23] N-(8'-Hydroxy-3',6'-dioxaoctyl)-13-aza-4,7,10,16,19,22-hexaoxapentacosane;

[24] N-(8'-Hydroxy-3',6' -dioxaoctyl)-14-aza-5,8,11,17,20,23-hexaoxaheptacosane;

[25] Those aminoalcohols having the structural formula: ##STR4## wherein m ranges from 1 to 3, and p ranges from 1 to 4; [26] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-5-aza-2,8-dioxanonane;

[27] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-6-aza-3,9-dioxaundecane;

[28] N-(11'-Hydroxy-3',6',9,'trioxaundecyl)-7-aza-4,10-dioxatridecane;

[29] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-8-aza-5,11-dioxapentadecane;

[30] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-8-aza-2,5,11,14-tetraoxapentadecane;

[31] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-9-aza-3,6,12,15-tetraoxaheptadecane;

[32] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-10-aza-4,7,13,16-tetraoxanonadecane;

[33] N-(11'-Hydroxy-'3',6',9'-trioxaundecyl)-11-aza-5,8,14,17-tetraoxaheneicosane;

[34] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-11-aza-2,5,8,14,17,20-hexaoxaheneicosane;

[35] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-12-aza-3,6,9,15,18,21-hexaoxatricosane;

[36] N-(11'-Hydroxy-3',6',9'-trioxaundecyl)-13-aza-4,7,10,16,19,22-hexaoxapentacosane;

[37] N-(11'Hydroxy-3',60',9'-trioxaundecyl)-14-aza-5,8,11,17,20,23-hexaoxaheptacosane;

[38] Those aminoalcohols having the structural formula: ##STR5## wherein m ranges from 1 to 3, and p ranges from 1 to 4; and [39] Those aminoalcohols having the structural formula: ##STR6## wherein n ranges from 1 to 3, and m also ranges from 1 to 3.

The present invention also relates to a process for the preparation of the polyoxaalkyl aminoalcohols having the structural formula [I].

Such process is characterized by reacting a polyalkylene glycol having the structural formula:

HO--CHR.sub.1 --CHR.sub.2 --O--CHR.sub.1 --CHR.sub.2 --O).sub.n H [II]

wherein R 3 , R 4 , R 5 and n are as defined above, with a bis(polyoxaalkyl)amine having the structural formula:

HN--(CHR.sub.3 --CHR.sub.4 --O).sub.m R.sub.5].sub.2 [III]

wherein R 3 , R 4 , R 5 and m are also as defined above, in a molar ratio of the polyalkylene glycol of formula [II] to the bis(polyoxaalkyl)amine of formula [III] of at least 1.5 times in excess of the stoichiometric amount required for preparation of the polyoxaalkyl aminoalcohols [I], at a temperature ranging from 120° to 220° C., preferably ranging from 150° to 200° C., and in the presence of a catalytically effective amount of a hydrogenation/dehydrogenation catalyst. The desired polyoxaalkyl aminoalcohol of formula [I] is thence conveniently separated from the mixture of reaction.

In a preferred embodiment according to the invention, a nickel catalyst is utilized, preferably of Raney nickel or Harshaw nickel type; the amount of catalyst advantageously ranges from 1 to 15% by weight of the amount of the bis(polyoxaalkyl)amine reactant [III], and preferably from 2 to 6% by weight thereof.

The molar ratio of the polyalkylene glycol [II] to the bis(polyoxaalkyl)amine [III] advantageously ranges from 1.5 to 10 times the stoichiometric amount thereof, and preferably from 2 to 6 times said stoichiometric amount.

The process according to the invention is advantageously carried out under a hydrogen atmosphere, or blanket, at a pressure of less than 20 bars, preferably at atmospheric pressure, and under vigorous agitation until the polyalkylene glycol has disappeared. The reaction characteristically takes from 2 to 10 hours for completion, typically from 3 to 4 hours. The amount of hydrogen advantageously utilized is on the order of 1 to 10% by weight of the polyalkylene glycol [II] and preferably is on the order of 1 to 5% by weight thereof.

The water formed during the course of the subject reaction may conveniently be eliminated from the reaction medium by means of a gaseous sweep, such as hydrogen, when employed, or nitrogen.

Exemplary of the polyalkylene glycol reactants [II] according to the invention are:

[1] Diethylene glycol;

[2] Triethylene glycol; and

[3] Tetraethylene glycol.

And exemplary of the bis(polyoxaalkyl)amine reactants [III] are:

[1] 5-Aza-2,8-dioxanonane;

[2] 6-Aza-3,9-dioxaundecane;

[3] 7-Aza-4,10-dioxatridecane;

[4] 8-Aza-5,11-dioxapentadecane;

[5] 8-Aza-2,5,11,14-tetraoxapentadecane;

[6] 9-Aza-3,6,12,15-tetraoxaheptadecane;

[7] 10-Aza-4,7,13,16-tetraoxanonadecane;

[8] 11-Aza-5,8,14,17-tetraoxaheneicosane;

[9] 11-Aza-2,5,8,14,17,20-hexaoxaheneicosane;

[10] 12-Aza-3,6,9,15,18,21-hexaoxatricosane;

[11] 13-Aza-4,7,10,16,19,22-hexaoxapentacosane;

[12] 14-Aza-5,8,11,17,20,23-hexaoxaheptacosane;

[13] Those bis(polyoxaalkyl)amines having the structural formula:

HN--(CH.sub.2 --CH.sub.2 --O).sub.m C.sub.p H.sub.2p+1 ].sub.2

wherein m ranges from 1 to 3, and p ranges from 1 to 4; and

[14] Those bis(polyoxaalkyl)amines having the structural formula:

HN--(CH.sub.2 --CH.sub.2 --O).sub.m C.sub.6 H.sub.5 ].sub.2.

Also consistent with the present invention, the subject polyoxaalkyl aminoalcohols are admirably well suited as cation complexing agents.

Representative of the cations conveniently complexed by the polyoxaalkyl aminoalcohols according to the invention are: NH 4 + and the cations of metals of the Groups IA to VIIA, VIII and IB to VB of the Periodic Table, and preferably the alkali or alkaline earth metal cations, e.g., Na, K, Li, Cs, Ca and Ba.

Moreover, complexation of the inorganic or organic salts of the immediately aforesaid metals, including the ammonium salts, with the subject polyoxaalkyl aminoalcohols gives rise to the solubilization of such salts, or markedly enhances the solubility of such salts in organic solvents, in which solvents or media said salts are typically insoluble, or only slightly soluble.

In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative.

Solubilization of KSCN

(1) Solubilization measured:

3380 mg/l

(2) Maximum calculated solubility:

3910 mg/l

(3) Degree of solubilization:

86.4%

(4) Complex formed:

##STR14##

______________________________________

The immediately aforesaid results are summarized in the Table I which follows:

______________________________________

Solubility

measured in

Solubility

the presence

measured

of the without the

Salt to be

Maximum calculated

complexing complexing

dissolved

solubility agent agent

______________________________________

LiSCN 690 mg/l 690 mg/l <1 mg/l

NaSCN 2300 mg/l 2300 mg/l <1 mg/l

KSCN 3910 mg/l 3380 mg/l <1 mg/l

______________________________________

Complexing ability of N-(5'-hydroxy-3'-oxapentyl)-8-aza-3,6,11,14-tetraoxapentadecane

Solubilization of alkali metal thiocyanates in methylene chloride

The test described in Example 6 was repeated, but using as the complexing agent the compound of Example 4:

The results were the following:

______________________________________

Solubility

measured in

Solubility

the presence

measured

of the without the

Salt to be

Maximum calculated

complexing complexing

dissolved

solubility agent agent

______________________________________

LiSCN 690 mg/l 670 mg/l <1 mg/l

NaSCN 2300 mg/l 2255 mg/l <1 mg/l

KSCN 3910 mg/l 3640 mg/l <1 mg/l

______________________________________

(a) Degree of solubilization of:

LiSCN: 97%

NaSCN: 98%

KSCN: 93%

(b) Complexes formed:

##STR15##

5,11,14-tetraoxapentadecane Solubilization of alkali metal thiocyanates

The test described in Example 6 was repeated, but using as the complexing agent to be tested the compound of Example 5:

The results were as follows:

______________________________________

Solubility

measured in

Solubility

the presence

measured

of the without the

Salt to be

Maximum calculated

complexing complexing

dissolved

solubility agent agent

______________________________________

LiSCN 690 mg/l 685 mg/l <1 mg/l

NaSCN 2300 mg/l 2300 mg/l <1 mg/l

KSCN 3910 mg/l 3640 mg/l <1 mg/l

______________________________________

(a) Degree of solubilization of:

LiSCN: 99%

NaSCN: 100%

KSCN: 93%

(b) Complexes formed:

##STR16##

While the invention has been described in terms of various preferred

embodiments, the skilled artisan will appreciate that various

modifications, substitutions, omissions, and changes may be made without

departing from the spirit thereof. Accordingly, it is intended that the

scope of the present invention be limited solely by the scope of the

following claims.